Insoluble heterocyclic disazo dyes

ABSTRACT

Heterocyclic disazo compounds containing two heterocyclicazoaniline groups of general formula WHERE D is a heterocyclic diazo component such as thiazolyl, benzthiazolyl, benzimidazolyl, etc. C AND D ARE SUCH SUBSTITUENTS AS METHYL, ETHOXY, PHENOXY AND ACYLAMINO R1 can be hydrogen, lower alkyl and lower alkyl substituted by cyano, phenyl, hydroxy, alkoxy, etc. R3 can be alkylene and substituted alkylene, etc. are bridged by a bridging group, Z, which has no dyestuff characteristics, such as -O-R5-O-, -NH-R5-NH- where R5 is aliphatic, cyclo- or araliphatic, aromatic or acyl, WHERE X&#39;&#39; is oxygen, sulfur or -NH and R6 is aliphatic, cycloaliphatic, aromatic or heterocyclic. The compounds are useful in dyeing synthetic fibers, especially polyester and acrylic.

United States Patent Peter et al.

[541 INSOLUBLE HETEROCYCLIC DISAZO DYES lnyentors: Richard Peter; Hans-Joerg Angliker,

both of Basel, Switzerland Assignee: Ciba-Geigy AG, Basel, Switzerland Filed: Aug. 7, 1970 Appl. No.: 62,165

Related US. Application Data Continuation-impart of Ser. No. 693,703, Dec. 27, 1967, abandoned.

[30] Foreign Application Priority Data Jan. 4, 1967 Switzerland ..77/67 May 26, 1967 Switzerland ..7468/67 Dec. 11, 1967 Switzerland ..17307/67 [52] US. Cl. ..260/158, 8/41 R, 8/41 A, 8/41 C, 260/152, 260/157, 260/160,

260/184, 260/187, 260/309.7, 260/326 C, 260/463, 260/465 D, 260/471 C, 260/475 P, 260/482 B, 260/490, 260/515 P, 260/520, 260/562 P, 260/570 R, 260/570.5 P

Int. Cl. .......C09b 33/16, D06p 3/54, D06p 3/72 Field of Search ..260/158, 146 R [56] References Cited UNITED STATES PATENTS 12/1962 Merian et a1. ..260/158 9/1966 Yamaya et al ..260/158 9/1968 Fisher et al ..260/ 158 12/1968 Fisheretal ..260/156 12/1969 Weaver et al ..260/158 151 3,691,148 45 Sept. 12, 1972 Primary Examiner-Floyd D. I-ligel Attorney-Harry Goldmsmith, Joseph G. Kolodny and Mario A. Monaco [57] ABSTRACT i-leterocyclic disazo compounds containing two heterocyclicazo-aniline groups of general formula where X is oxygen, sulfur or NH and R, is aliphatic, cycloaliphatic, aromatic or heterocyclic. The compounds are useful in dyeing synthetic fibers, especially polyester and acrylic.

5 Claims, No Drawings INSOLUBLE HETEROCYCLIC DISAZO DYES CROSS-REFERENCE TO A RELATED APPLICATION This application is a continuation-in-part of our application Ser. No. 693,703, filed Dec. 27, 1967, and now abandoned.

The present invention provides new and valuable disazo dyestuffs of the formula in which R, and R, each represents a hydrogen atom or preferably an alkyl group, each of which may be bound to residues A, and A respectively in ortho-position to the nitrogen atoms directing coupling to form a ring, R, and R each represents an alkylene group which binds the nitrogen atom to Z preferably through at least two carbon atoms, the groups NR,R,Z--R NR -NR,--,Z or NR,R,--Z- being capable of forming a perhydropyrazine residue, A, and A, each represents a para-phenylene residue, D, and D; each represents the residue of a diazo component that may be quaternated and that preferably does not contain heterocyclic rings and/or quaternatable hetero atoms, and Z represents a divalent bridging group preferably containing at least one hetero atom and which does not have dyestuff characteristics, which group, when D, and/or D, represent(s) a heterocyclic group and/or contain(s) a quaternatable hetero atom, is preferably (1) free from ether or CN C bonds and/or (2) is not a divalent hydrocarbon residue. The invention also includes mixtures of the new dyestuffs one with another and mixtures of the new dyestuffs with other azo dyestuffs. The compounds may be further defined as a hetero-cyclic disazo dyestuff of the formula d ai wherein R, and R, are each selected from the group consisting of hydrogen, alkyl containing up to four carbon atoms, cyanoethyl, benzyl, phenethyl, hydroxyethyl, alkoxyalkyl containing up to six carbon atoms, hydrocarbylcarbonyloxyalkyl containing up to seven carbon atoms, chloroethyl, [3, B, fi-trifluoroethyl, dihydroxypropyl, carbomethoxypropyl, carboethoxypropyl, acetylaminoethyl, formylaminoethyl, flmethanesulfonylethyl, fl-ethanesulfonylethyl, B- (parachlorobenzenesulphonyl)-ethyl, alkyloxy-carbonyloxyalkyl containing up to six carbon atoms, B-carboxyethyl, B-acetylethyl, ,B-diethylarninoethyl and B- cyanoacetoxyethyl; c and d independently are hydrogen, C,-C,-alkyl, C,C,-alkoxy, phenoxy or thiophenoxy', and c additionally is chlorine, bromine, trifluoromethyl, methylsulphonyl, phenoxycarbonyl, methoxycarbonyl, aminocarbonyl, monocarboxylic acylamino of up to four carbon atoms, acylamino derived from the residue of methane-, ethaneor paratoluene-monosulfonic acid, phenoxycarbonylamino, methoxycarbonylamino or aminocarbonylamino; R, and R, are alkylene containing up to three carbon atoms, B-hydroxypropylene or fi-acetoxypropylene; Z

o o l(CH:)n-1 1O wherein n is from 2 to 8; D, and D, are each selected from the group consisting of thiazolyl and substituted thia'zolyl wherein the substituent is selected from the group consisting of nitro, methylsulfonyl, cyano, methyl, phenyl, chlorophenyl, nitrophenyl and thiocyano; benzthia'zolyl and substituted benzthiazolyl wherein the substituent is selected from the group 'eonsistingof methyl, methoxy, ethoxy, chloro, bromo, cyano, nitro, carboethoxy, methylsulfonyl and methylcarbonyl; pyridyl, quinolyl, pyrazolyl andsubstituted pyrazolyl wherein the substituent is selected from the group consisting of methoxyphenyl, pheny], cyano and nitrophenyl; indazolyl, triazolyl and substituted triazolyl wherein the substituent is selected from the group consisting of methyl, ethyl, phenyland benzyl, thiadiazolyl and substituted thiadiazolyl wherein the substitnent is selected from the group consisting of phenyl, methyl, methylsulf0 and pyridyl; thienyl, nitrothienyl, methylsulfothienyl, methoxyisothiazolyl, bermoxazolyl, N-methylbenzpyrazolyl, benzimidazolyl, N-methylbenzimidazolyl 40 and chlorobenzimidazolyl; m is l or 2 and X, is an anion; said dyestuff being free sulphonic acid groups.

The residues of the monoazo dyestuffs are preferably bound through the group of the formula in whichp=l or 2, R and R have the meanings ascribed to them in formula (1),

so A represents a divalent organic residue containing at least one acyl group or, if necessary, a residue of the formula and E represents the residue of a diepoxy compound in which the two oxirane groups of the formula is preferably a member of the organic chain joining groups R, and R When the residues of the monoazo dyestuffs are bound through the group E, the residues R, and R bound to the nitrogen atoms of the monoazo dyestuffs which direct coupling are B-hydroxyethyl groups which are formed by addition of the two oxirane groups of the diepoxy compounds to the amino groups which direct coupling and which contain at least one reactive hydrogen atom.

Of the dyestuffs which are bound through a bridging group of the formula -R,(A);, (51);; R special mention is made of those in which the residues of the formula D, and/or D, are quaternated.

The new dyestuffs may be obtained, for example, either by (a) reacting azo dyestuffs of the formulae which contain a reactive hydrogen atom bound to an amino group, with a bifunctional compound of the formula in which it stands for l or 2 and Y represents a reactive negative residue, preferably a halogen atom, when n 2, and a reactive residue of the formula --Cl-l CH,

capable of additive combination when n l, to form the dyestuffs of the invention of the formula (1), or (b) reacting the dyestuffs of the formulae in which E, and E, represent groups containing reactive oxirane groups, preferably glycidyl residues, or groups containing double bonds capable of additive reaction, with bifunctional reactive compound to form the dyestuffs of the invention of the formula (1), or (d) reacting the coupling components of the formulae with the bifunctional reactive compound of the formula 2' to form the compounds of the formula and then coupling them with the diazonium compounds of the diazo components D,NH and D,NI-l,to form the disazo compound of the formula l or (e) oxidizing the azo dyestuffs of the formulae which are indicated under (b), to form a dyestuff of the formula (1), which may done when X, and X, in the above formulae each represents an SH group; in which case 2 then represents a bridging group of the formula SS--. If desired, the disazo dyestuffs so obtained may be quatemated at one of the residues D, or D, when the latter contain groups capable of quaternation; this may be effected in the customary manner with an alkylating agent, or, if desired, at least a molar proportion of an already quaternated diazonium compound may be used when coupling with the bifunctional coupling component.

The components represented by A, B, R, and R,, as well as R, and R, may be identical, with the result that symmetrical disazo dyestuffs are obtained, or starting materials may be used in which one or more of these components are different so that mixtures of disazo dyestuffs are obtained.

The new dyestuffs are preferably free from sulphonic acid groups. When they do not contain quaternated groups they are either insoluble or sparingly soluble in water and belong to the clisperse" class of dyestuffs. Dyestuffs of this group which are specially preferred are those in which the diazo component does not contain nitrogen atoms capable of quaternation and which is derived, for example, from a negatively substituted aniline.

However, when the dyestuffs contain quatemated diazo components of the formula D, and/or D,, they are soluble in water and must not contain carboxylic or sulphonic acid groups.

Mixtures of disazo and monoazo dyestuffs that may also be mentioned are those obtained by coupling a bifunctional coupling component of the above mentioned formula HA,NR,R,Z-R NR, A,H with less than two mols of a diazo compound of the formula D-N NCl.

Azo dyestufls that may be mentioned as being suitable for processes (a) and (b) are those obtained by coupling diazo compounds of amines free from carbonyl and sulphonic acid groups, preferably those belonging to the aromatic or heterocyclic series, with any desired coupling components free from carbonyl and sulphonic acid groups, it being essential that the coupling component contain an active NH group or a reactive atom bound to an N-alkyl residue or a reactive group of the kind defined above.

The diazo residues D, l and D, may be aromatic residues which are preferably free from heterocyclic rings and/or hetero atoms capable of quatemation. However, the said residues may also be capable of quatemation or they may be quaternated. when the monoazo dyestuffs are to be reacted afterwards with bifunctional alkylating or acylating agents to fonn the disazo dyestuffs, the residue D must also be free from reactive acylatable or alkylatable hydrogen atoms. When coupling is carried out in the last step, D,-N N-Cl and D,N N-Cl are general identical.

D,NI-l, and D,NH, to be used as diazo components are preferably aminobenzenes, especially those of the formula in which represents a hydrogen or a halogen atom or an alkyl, alkoxy, phenoxy, nitro, cyano, carbalkoxy or alkylsulphone group and b represents a hydrogen or a halogen atom or an alkyl, cyano or trifluoromethyl group.

The following are given as examples: aminobenzene, l-amino-4-chlorobenzene, l-arnino-4-bromobenzene, l-amino-4-methylbenzene, l-amino-4-nitrobenzene, lamino-4-cyanobenzene, l-amino-2,5-dicyanobenzene, l-amino-4-methylsulphonylbenzene, l-amino-4-carbalkoxybenzene, l-amino-ZA-dichlorobenzene, lamino-2,4-dibromobenzcne, l-amino-2-methyl-4- chlorobenzene, l-amino-2-trifluoromethyl-4- chlorobenzene, l-amino-ZtyanoA-chlorobenzene, lamino-2-carbomethoxy-4-chlorobenzene, l-aminoJ- carbomethoxy-4-nitrobenzene, l-aanino-Z-chlorolcyanobenzene, l-amino-Z-chlorol-nitrobenzene, amino-2-chloro-4-carbethoxybenzene, l -amino-2- chloro-A-methylsulphonyl-benzene, l-amino-Z-methylsulphonyl-4-chlorobenzene, l-amino-2-methylsulphonyl-4-nitrobenzene, l-amino-2,4-dinitrobenzene, 1- amino-2,4-dicyano-benzene, l-amino-2-cyano-4- methylsulphonylbenzene, l-arnino-2,6-dichloro-4- cyanobenzene, l-amino-2,6-dichloro-4-nitrobenzene, l -amino-2,4-dicyano-6-chlorobenzene, l-amino-2,4- dinitro-6-chlorobenzene and especially l-amino2- cyano-4-nitrobenzene; also l-aminobenzene-Z, -3- or 4-sulphonic acid amides, for example, N-methylor N,N-dimethylor -diethyl amide.

Amines from the series of heterocyclic diazo components are preferably used when the group Z contains an acyl group or especially the diacyl residue of a difunctional acid, or at least two Z-(hydroxy or acyloxy )-propylenel ,3 groups.

The heterocyclic diazo component may be any desired diazotizable heterocyclic amine which is free from acidic substituents imparting solubility in water, but especially the amines which contain a five-membered heterocyclic ring having two or three hetero atoms, especially one nitrogen atom and one or two sulphur, oxygen or nitrogen atom(s).

The following are given as examples of heterocyclic diazo components: Z-aminothiazole, Z-amino-S- nitrothiazole, Z-amino-S-methylsulphonylthiazole, 2- amino-S-cyanothiazole, 2-amino-4-methyl-5- nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4- phenylthiazole, 2-amino-4-(4'-chloro)-phenylthiazole, 2-amino-4-(4'-nitro)-phenylthiazole, 3-aminopyridine, 3-arnino-quinoline, 3-aminopyrazole, 3-amino-l-phenylpyrazole, 3-amino-indazole, 3-amino-l,2,4-triazole, 5-(methyl-, ethyl-, phenylor benzyl-)l,2,4-triazole, 3- amino- 1 -(4'-methoxyphenyl)-pyrazole, 2-

aminobenzthiazole, 2-amino6-methylbenzthiazole, 2- amino--methoxybenzthiazole, 2-amino-6- chlorobenzthiazole, 2-amino-6cyanobenzthiazole, 2- amino-6-thiocyanothiazole, 2-amino-6- nitrobenzthiazole, 2-amino-6-carboethoxybenzthiazole, Z-amino -(4- or 6)-methylsulphonylbenzthiazole, 2-amino-l,3,4-thiadiazole, Luminol,3,5-thiadiazole. 2-amino4-phenylor -4-methyll ,3 ,S-thiadiazole, 2-amino-5-phenyll ,3 ,4-thiadiazole. Z-amino-3-niu'o-5-methylsulphothiophene, 2-amino- 3,$-bis-(methylsulphoythiophene, 5-amino-3- methylisothiazole, 2-amino-4-cyanopyrazole, 2-(4' nitrophenyll-3-arnino-4-cyanopyrazole and 3- or 4- aminophthalimide.

In addition to the above heterocyclic diam components which are capable of quaternation, the following diazo components capable of quaternation are of interest: meta'di-(methyl or ethyl)-aniline and paraaminobenzoic acid-N-[meta-di-(methyl or ethyl)- aminophenyll-amide.

Diazotization of the above-mentioned diam components may be carried out by known methods, for example, with a mineral acid and sodium nitrite, or, for example, with a solution of nitrosylsulphuric acid in concentrated sulphuric acid.

Coupling may also be carried out in known manner, for example, in a neutral to acid medium, if necessary, in the presence of sodium acetate or a similar buffer which influences the rate of coupling, or a catalyst, for example, dimethylfonnamide or pyridine or a salt thereof.

Coupling may also be effected advantageously by combining the components in a mixing nozzle. By mixing nozzle" is meant a device in which the liquids to be mixed are combined with one another in a comparatively small space, whereby at least one of the liquids is conducted through a nozzle, preferably under pressure. The mixing nozzle may be constructed and operated, for example, on the principle of the water jet pump, the supply of one of the liquids to the mixing nozzle corresponding to the supply of water in the water jet pump, and the supply of the other liquid corresponding to the connexion between the water jet pump and the vessel to be evacuated; feed of the liquid through the latter supply route may also be effected under pressure.

However, it is also possible to use other devices to effect rapid and, if necessary, continuous mixture in a small space.

After coupling, the non-quaternated dyestuffs that are formed can easily be separated from the coupling mixture, for example, by filtration, because they are virtually insoluble in water. When the dyestuffs obtained are quatemated, they may be salted out.

The residues A, and A, of the coupling components are naphthylene and especially phenylene groups bound in 1,4-position and which preferably do not contain alkylatable or acylatable hydroxy, mercapto or primary or secondary amino groups.

Examples that may be mentioned are l,4phenylene groups of the formulae c,, c d, and d, each represents a hydrogen atom or a methyl, ethyl, methoxy, ethoxy, thiophenoxy or phenoxy residue.

The groups c, and c, are preferably bound in orthoposition to the azo group and, in addition to the abovementioned groups, may also represent a chlorine or a bromine atom, a trifluoromethyl group, an alkylsulphonyl group, preferably a methylsulphonyl group, or an acylamino group that may be alkylated, preferably methylated, at the nitrogen ato and in which the acyl residue is the residue of an organic monocarboxylic acid, such as propionic, formic or butyric acid, or of an organic monosulphonic acid, for example, methane-, ethaneor para-toluenemonosulphonic acid, or of a carbarnic or carbonic acid monoester or monoamide, for example, phenoxy-carbonyl, methoxycarbonyl or aminocarbonyl.

The groups 4 and d, are preferably in ortho-position to the amino group directing coupling.

The groups R, and R, may be hydrogen atoms or low alkyl groups containing one to four, but preferably two to four, carbon atoms, for example, methyl, ethyl, npropyl or n-butyl groups which may be substituted in the usual manner, for example, halogenated alkyl groups, for example, fi-chloroethyl, 3,8,3- trifluoroethyl or Bqr-dichloropropyl groups, cyanoethyl groups, alltoxyallryl groups, for example, 5- ethoxyethyl or G-methoxybutyl groups, hydroxyalkyl groups, for example, fl-hydroxyethyl or B,y-dihydroxypropyl groups, phenylalkyl groups, such as bermyl or phenylethyl groups, carbalkoxy groups, for example, hydrocarbylcarbonyloxyalkyl groups containing up to 16 carbon atoms, preferably up to seven carbon atoms, such as acetyloxyethyl, butyryloxyalkyl, formyloxyalkyl, p-phenoxy-benzoyloxy alkyl or benzoyloxyalltyl, B- or y-carbo-(methoxy-or ethoxy)-propyl groups, acylaminoalkyl groups, for example, fl-(acetylor formyl)-aminoethyl groups, fi-(allryior aryl )-sulphonylalkyl groups, for example, B-methanesulphonylethyl, B- ethanesulphonylethyl or fl-(parachlorobenzenesulphonylJ-ethyl groups, alkylor arylcarbamoyloxyaikyl groups, for example, fi-methylcarbamyloxyethyl or B-phenylcarbamyloxy-ethyi groups, alkyloxy-carbonyloxyalkyl groups, for example, 3- (methoxy-, ethoxyor isopropyloxy)-carbonyloxyethyl groups, and y-acetamidopropyl, B-(para-nitrophenoxn w B-(p y yP y)-= y B4B- acetylethoxycarbonyll-ethyl, B-[fl'-(cyano-, hydroxy-, methoxyor acetoxy)-ethoxycarbonyl]-ethyl, cyanoalkoxyalkyl, B-carboxyethyl, B-acetylethyl, B- diethylaminoethyl and B-cyanoacetoxyethyl groups. These groups generally contain not more than eight, but preferably not more than six, carbon atoms.

The groups R, and R are alkylene groups that may be substituted, for example, unsubstituted ethylene groups, or, in accordance with a special embodiment of the invention, alkylene groups hydroxylated in fi-position to the amino group directing coupling, which alkylene groups may also comprise part of an alicyclic ring system. The latter are formed, for example, in the two-sided reaction between diepoxides, especially diglycidyl compounds, and the amino groups of the coupling components which direct coupling and which carry at least one reactive hydrogen atom, or the corresponding azo dyestuffs which are formed. The

hydroxyl groups in fl-position which are formed may be substituted, whereby the substituents. together with the hydroxyethyl groups which lead to the nitrogen atom directing coupling, may have the same meaning as the groups R, and R. defined above, provided they are derivatives of an N-hydroxyethyl group starting from the nitrogen atom which directs coupling.

When the residue R or R. in the dyestufl's of the invention is bound to the para-phenylene residue of the corresponding coupling component R, or R, in orthoposition to form a ring, the coupling component used, for example, is tetrahydroquinoline or benzmorpholine or derivatives thereof.

Suitable coupling components of this kind are, for example, l,2,3,4-teuahydroquinolines (generally abbreviated to tetrahydroquinolines) and benzornorpholines, for example, tetrahydroquinoline, N-B'hydroxyethyltetrahydroquinoline, N-fl,ydihydroxypropyltetrahydroquinoline, N- ,y-dihydroxypropyl-l-methoxytetrahydroquinoline, N-B dihydroxypropyl-S-acetylamino-tetrahydroquinoline, N-fl-hydroxyethyl-Z,2,4-trimethyltetra-hydroquinoline, N-fl-hydroxyethylbenzomorpholine and Isl-5,7 dihydroxypropyl-S-acetylaminobenzomorpholine.

When residue R, and residue it, each represents a methylene group, the group Z forms an alkylene residue of the formula -CHX,=, in which X, represents a hydroxyl group or a bromine or a chlorine atom.

Preferably, the nitrogen atoms directing connected through at least five atoms.

Substituted anilines, which may be used in the synthesis of bifunctional coupling components in accordance with process (c), are, for example, the following compounds, in which the group X has the same meaning as Xi and X, above:

CH: Q-NHCzHtX.

CiHrX CrHi CrHiCN onnocoon, 0,11,

OCH:

coupling are CsHsCOOCHi CIII! l NHCOCH:

CzlllX CsHqCN The bridging group Z which has nodyestuflscharacteristics isprincipally a group corresponding tonne of the following formulae: S, SS, NH--,

I Ulla especially groups containing acyl residues which "correspond to the formulae -*0C0--, -*0C60-, 0COC00, Nl-lC0-, C0NH-, --'GONHGO-, CONHNHCO- and NHCOCONH, as well as the colorless connecting group of the formula X'COR COX'-, in which X represents an oxygen or a sulphur atom or an Nl-l group and R, represents an aliphatic, cycloaliphatic, aromatic or heterocyclic residue, preferably an ethylene or apara-, metaor orthophenylene residue, the colorless connecting group of the formula X'--C0--NHR NHCO--X', in which X represents an oxygen or a sulphur atom or an Nl-l group and R represents an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic residue of a diisocyanate, preferably an ethylene, hexarnethylene, para-phenylene or toluylene residue, or a residue of the formula the colorless connecting group of the formula 0COX'R X'0C0-, in which X has the meaning given above and R, represents a divalent organic residue, especially an aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic residue, which may be interrupted by the groups X; when X is an NH- group, R, has the same meaning as R and the colorless connecting group of the formula X"SO,- R,-S0,X", in which X" represents an oxygen or a nitrogen atom (the nitrogen atom may be substituted) and R, represents an aliphatic or aromatic residue.

The connecting group Z is introduced as follows:

The linkage with dicarboxylic acid esters is effected by known methods, for example, by esterification, especially with azeotropic elimination of water, by trans-esterification with elimination of a volatile alcohol or phenol or by reaction-with dicarboxylic acid anhydrides, by reaction with dicarboxylic acid anhydrides, by reaction with dicarboxylic acid halides, whereby the tertiary amino group present in the coupling component may take up the hydrogen halide that is liberated. In addition to the purely organic acid chlorides, the phosphorus-organic alkanephosphoric acid dichlorides may also be used, for example, ethaneor cyclohexanephosphonic acid dichloride. To prepare the dicarbamic acid esters, reaction is further effected with diisocyanates, when the group X is a hydroxyl group, it being advantageous to carry out the reaction either in an inert solvent or without a solvent at a moderate temperature, however, an active solvent may also be used.

Also included in the class of organic acid chlorides is phosgene, with which the carbonates are obtained; a method of carrying out the reaction is first to react the hydroxyl group of the dyestuff component with at least one mol of phosgene to form the chloroformic acid ester and then to additively combine the ester witha diol or an unsubstituted or partially substituted diamine. l-iowever the carbonicacid esters may also be prepared by reaction with dialkyl or diaryl carbonates.

When X is van amino group containing at least one active hydrogen atom, the corresponding dicarboxylic acid amides are obtained preferably by reaction with dicarboxylic acid halides, and the corresponding phosphoric acid diamides are obtained by reaction with alltanephosphoric acid dichlorides. The corresponding areas are obtained by reaction with diisocyanates. The corresponding bis-carbamic acid esters are obtained by reacting the dyestufl component with an equimolar amount of a bis-chloroformic acid ester.

When Z is the residue of a dicarboxylic acid, the following free acids, or the halides and anhydrides thereof (if the acid is capable of forming an anhydride) or esters thereof with volatile alcohols, are used as starting materials serving as bifunctional reactants corresponding to the group X: oxalic acid, succinic acid, malonic acid, pimelic acid, adipic acid, methyladipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, chlorofumaric acid, allylsuccinic acid, dodecylsuccinic acid, diglycollic acid, methylene-bis-thioglycollic acid, 2,3-dibromsuccinic acid, thiodibutyric acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene-tetrahydrophthalic acid, methylenendomethylenetetrahydrophthalic acid, hexachloroendomethylenetetrahydrophthalic acid, phthalic acid,

isophthalic acid, terephthalic acid, 2,5-thiophenedicarboxylic acid, furandicarboxylic acid and the dicarboxylic acids of the formulae "000 COOH H 0 Q-O-s m-O-c OOH noocO-GIh-OOo-cm-O-coou For linkage with the acyl residue of a disulphonic acid there are used the halides of aliphatic and especially aromatic disulphonic acids.

Aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclie diisocyanates are suitable as diisocyanate components that form the colorless connecting group 2 by reaction with 2 mols of the dyestuff component of the formula D,-N NA,NR,R,X. The following are given as examples: hexamethylenediisocyanate, N,N'-bis-(4-methyl-3-isocyanatophenyl) urea, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, l ,2,3,4,5,G-hexahydrodiphenylmethane-4,4 diisocyanate, and also aromatic dibocyanates, for example, toluene-2,4- or -2,6-diisocyanate or mixtures thereof, phenylene-l,4-diisocyanat bis-(4-methyl-3- isocyanatophenyl)-carbodiimide, diphenyl-4,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane 3,3'-diisocyanate, diphenyldimethylmethane- 4,4'-diisocyanate, stilbene-4,4-diisocyanate, benzophenone-4,4'-diisocyanate, diphenyletheror diphenylsulphide-diisocyanate, as well as the substitution products thereof, for example, with derivatives substituted by alkyl, alltoxy, halogen or nitro groups, for example, 3,3'-dimethylor 3,3' dimethoxyor 3,3' dichlorodiphenylmethane-4,4'-diisocyanate. Further examples are diisocyanates of the naphthalene series, for example, naphthylene-l,5-diisocyanate, or heterocyclic diisocyanates, for example, those of benzofuran or urea, and diisocyanates containing uretdione groups, for example, l,3-bis-(4'-methyl-3'-isocyanatophenyl)- uretdione.

Symmetrical diisocyanates, for example, diphenyl- 4,4'- or diphenylmethane-4,4'-diisocyanate, are preferred.

If desired, the diisocyanates may also be prepared in situ, for example, by reacting bis-chloromethylbenzenes and sodium or lead cyanate in an active solvent.

The manufacture of the carbonates when X is a hydroxyl group may be carried out either by effecting the reaction directly with phosgene to form the carbonate, if necessary, in the presence of a quaternary ammonium base or salt, or by first producing the chloroformic acid ester of an azo dyestuff residue and reacting it either with the same azo dyestuff residue or with a further azo dyestuff residue containing a free hydroxyl group to form the carbonate. On the other hand, 2 mols of the chloroformic acid ester may be reacted, preferably in the presence of a hydrogen chloride acceptor, for example, pyridine, with 1 mol of a diol, a diamine or a dithiol to form the diurethane, bis-( thiourethane) or bis-urea compound.

The following hydroxyl compounds are given as examples of suitable divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl compounds in which the hydrocarbon skeletal structure may be interrupted by hetero atoms: l,2-dihydroxyethane, 1,2- or 1,3- dihydroxypropane, 1,2- or 1,3- or 1,4- or 2,3-dihydroxybutane, l,2- or 1,3- or 1,4- or 1,5- or 2,3- or 2,4- dihydroxypentane, the corresponding dihydroxyhexanes, heptanes, -octanes, -nonanes, -decanes, -undecanes, -dodecanes, -hexadecanes and -octadecanes, l ,4-dihydroxybutene, 1,4-dihydroxy-2-methylbutane, 1 ,5-dihydroxy-2,2-dimethylpentane, l,5-dihydroxy- 2,2,4-trimethylpentane, di-(B-hydroxyethyl)-thioether, di-(B-hydroxyethyD-ether diglycol), triglycol, cyclohexanediol-l,2- or [,3- or 1,4, 4,4'-dihydroxydicyclohexylmethane, 4,4'-dihydroxydicyclohexylmethylmethane, 4,4'-dihydroxydicyclohexyldirnethylmethane, 4-hydroxybenzylalcohol, l,4-di-(B-hydroxyethoxy)-benzene, l,2- or 1,3- or: 1,4-dihydroxybenzene, l-rnethyl-2,4- (or 2,3- or 3,4- or 2,6- or 2,5- or 3,S)-dihydroxybenzene, i,3-dimethyl-2,4- (or -4,6- )-dihydroxybenzene, l ,4-dirnethyl-2,5-dihydroxybenzene, l-ethyl-2,4-dihydroxybenzene, l-isopropyl- 2,4-dihydroxybenzene, 4,4-dihydroxyazobenzene, 2,4-

or 4,4'-dihydroxydiphenylether, 2,2'-dihydroxyethyleneglycoldiphenylether, 1,3- or 1,4- or 1,5- or 1,6- or 1,7- or 1,8- or 2,6 or 2,7-dihydroxynaphthalene, 4,4-dihydroxydiphenylamine, 2,4'- or 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethylmethane, 4,4- dihydroxydiphenyldimethylmethane, i,l'-di-(4'- hydroxyphenyl)-cyclohexane, 4,4'-dihydroxydiphenyl- (di)-sulfide and 4,4'-dihydroxydiphenylsulphone or mixtures of such diols.

Instead of diols, dithiols may be used, especially aliphatic, araliphatic and aromatic dithiols, for example, l,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol, 3 ,4-toluenedithiol and para-xylyienedithiol.

Suitable amines having two primary or secondary nitrogen atoms which may be reacted with two mols of the azo dyestuff chloroformic acid ester of the formula are l,2-diaminoethane, 1,2- or 1,3-diaminopropane, l,2- or 1,3- or 1,4- or 2,3-diaminobutane, 1,2- r 1,3 or 1,4- or 1,5- or 2,3- or 2,4 diaminopentane, the corresponding diaminohexanes, -heptanes, -octanes, nonanes, -decanes, -undecanes, -dodecanes, -hexadecanes and -octadecanes, 1,4-diaminobutene, l,4- diamino-Z-methylbutane, l,5-diamino-2,2-dimethylpentane, l,S-diamino2,2,4-trimethylpentane, di-(B- aminoethyl)-thioether, di-(y-aminopropyl)-ether, di- (y-aminopropyD-thioether, di-(w-aminohexyhthioether, N,N'-dimethyldiaminoethane-l,2, N',N' diethyldiaminoethanel ,2, l-amino-3- methylaminopropane, isophoronediamine, piperazine, N-laminoethylpiperazine, 4-aminopiperidine, (I, O'-

diamino-l,3-(or 4,4) -dimethylbcnzene, 0, fldiamino-l,4-(or -l,2) -dimethylcyclohexane, O. Q'- diamino-l,4-diethylbenzene, 0., (l-diamino-l,4- (or l,5)-dimethylnaphthalene, ll, Q-diamino-di-n-propylbiphenyl, l,2- or 1,3- or l,4-diamino-cyclohexane, lmethyl-2,4-diaminocyclohexane, l-ethyl-2,4r-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4- diaminodicyclohexylmethylmethane, 4,4- diaminodicyclohexyldi-methylmethane, 4,4'-diamino- 2,2-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'- dimethyldicyclohexylmethane, 4-aminobenzyl-amine, 2-(4'-aminophenyl)- l -aminoethane, 1-( 3 '-arninophenyl)-l-aminoethane, 3-(3- or 4'-aminophenyl)-laminopropane, 3-(3'- or 4'-aminophenyl)-l-aminobutane, tetrahydronaphthylenediamine-l,5 or -l,4, hexahydrobenzidine-4,4'-diarnine, hexahydrodiphenylmethane-4,4'-diamine, l,2-, l ,3- or l,4- diaminobenzene, l-methyl-2,4- (or 2,3- or 3,4- 01' 2,6- or 2,5- or 3,5 )-diaminobenzene, l,3-dimethyl-2,4- (or 4,6)-diaminobenzene, l ,4 -dimethyl-2,5- diarninobenzene, l-ethyl-2,4-diaminobenzene, lisopropyl-2,4-diaminobenzene, diamino-diethylbenzene, diisopropyl-diamino-benzene, l-chloro-2,4- diaminobenzene, l,3-dichloro-2,4- (or -4,6)- diaminobenzene, l,4dichloro-2,5-diaminobenzene, 2,4-(or 4,4)-diaminodiphenylether, ethyleneglycoldiphenylether-2,2'-diamine, diethyleneglycoldiphenylether-2,2'-diamine, N,N'-dimethylphenylenediaminel ,3or l ,4, N-methylphenylenediamine- 1,4, 1,3- or l,4- or l,5- or 1,6- or l,7- or 1,8- or 2,6- or 2,7-naphthylenediamine, l ,l '-dinaphthyl-2,2'-diarnine, 4,4'-diaminodiphenylamine, 2,4'- or 4,4- diaminodiphenyl, 3 ,3 '-dimethyl-4,4'-diaminodiphenyl, 2,2'- or 3,3'-dichloro-4,4'-diaminodiphenyl, 4,4- diaminodiphenylmethane, 4,4 diphenylmcthylmethane, 4,4'-diaminodiphenyldimethylmethane, 2,2- dimethyl-4,4 '-diaminodiphenylmethane, l l -di-(4'- aminophenyD-cyclohexane, l, l -di-(4'-amino-3'- methylphenyl)-cyclohexane, 3,3- diaminobenzophenone, 2,4-diarninodiphenylethanel ,2,4,4',4' triaminotriphenylmethane, 4,4'-diamino- 2 ,2 ,5 ,5 '-tetramethyltriphenyhnethane, 4,4'-diamino- 2,2 ,5 ,5 '-tetramethyl-2 '-chlorotriphenylrnethane, fluorenediamine-2,7,2,6-diamino-anthraquinone, 9 ethylcarbazole-Ii,6-diamine, pyrene-3,8-diarnine, chrysene-2,8-diamine, benzidinesulphone-4,4- diamine, diphenylsulphide-2,4-diamine, diphenyldisulphide-4,4'-diamine, diphenylsuiphone-4,4' diamine, diphenylmethanesulphone-4,4'-diamine, 4-methyl-3- aminobenzenesulphonic acid-(4'-aminophenyl-ester, di( 4-aminobenzenesulphonyl )ethylenediamine-3 ,3 dlmethoxy-4,4-diaminodibenzylthioether, 4,4- dimethoxy-3 ,3 '-diaminobenzenethioethyleneglycol and 3 ,3 'dimethoxy-4,4'-diarninobenzylsulphone.

In addition to dialcohols, dithiols and diamines, difunctional compounds may be used in which the two functional groups (of the kind defined above) are different from each other.

Dyestuffs containing ether bridges or the residue OR"--O as used in accordance with the invention may be obtained, for example, by reacting two molecules of a dyestuff of the formula D'-N N- A,NR,-R,-OH with one mole of a dihalide. Corresponding dyestuffs joined through amino bridging groups may be obtained by reacting two molecules of a dyestufl' of the formula D -N NA NR R, NH, with one moi of a dihalide. When starting from dichlorides, it is advantageous to use dihalldes having active chlorine atoms. Suitable dlhalides are, for example, l,4-dichlorobutene, di-fi-chloroethylether, dichloroethylformaldehyde and the isomers of bis- (chloromethyD-benzene.

When the group 2 is produced by the linking of two azo dyestuff molecules of the formulae D,N N- A,--Nl-l-R, and Dg-N N-- A,Nl-l-R,, which are preferably identical, to a molecule of a bifunctional compound containing two double bonds capable of additive reaction, the starting materials used may be com pounds containing two dihydropyranyl rings capable of additive reaction, for example, as-described inBritish Pat. Specification No. 996,705.

lf daired, divinylsulphone may be used as bifunctional compound containing two double bonds having additive capacity, in which case dyestuffs are obtained in which the nitrogen atoms directing coupling are connected through the bridging group of the formula CH,-CH,-ZCH;C-H and Z is a sulphonyl group.

Dyestuffs in whichZ is a sulphonyl group may also be obtained by coupling a compound of the formula 1-!- Ay-NR1CH -sOg-CHgCHg-NRg-Ar- H, described in British Pat. Specification No. 1,076,380with 1,076,380, didzo components described above.

To-manufacture dyestuffs of the type-last mentioned, monoazo dyestuffs may be used as starting materials which contain a reactive vinylsuiphoneethyl group bound to the nitrogen atom directing coupling, as described, for example, in Belgian Pat. Specifications Nos. 685,628, 685,765, 685,766 and 685,768. The reactive vinyl group, which is present in the abovementioned dyestufis, may be reacted with another dyestufl' of the formula D-N N-A-NHR, to form the dyestufi's of the invention of the formula (1). In this manner two different monoaao dyestuffs may be joined together. It is preferable that there is no sulphonyl group present in the group of the formula Z in the dyestufi's of the invention.

Disazo dyestuffs in which two different monoazo dyestuff residues are joined together through an acyl group may be obtained, for esampleby first reacting one molecule of a dyestuff of the formula D,-N N A --NR,-R,X,, in which X, represents a mercapto, a primary or secondary amino or a hydroxyl group, with one molecule of a diisocyanate containing iso' cyanate groups of diflerent reactivity, for example, 2,4- toluylene-diisocyanate or isophoroned-iisocyanate, and then with one molecule of a dyestuff of the formula D,--N N-A,-NR,R -X,, in which X, has the same meaning as X,.

Furthermore, a monoam dyestuff of the formula D,N NA NR,R 0l-l may be reacted with phosgene to form the chloroformic acid ester whi h is then reacted with a second monoazo dyestuff of the formula D,N N-A,NR,-R X, in which X represents a mercapto, amino or hydroxyl group, to form the carbonic acid derivative.

When the two dyestuff residues of the formula D-N NANRlR X', in which the reactive group X in this case is preferably a carboxyl or an amino group, are reacted with a diepoxide, the

'ether bridges; in this reaction, hydroxyl groups are simultaneously formed in B-position to the carbon atoms bound to the two ether bridges, their formation being brought about by the opening of the epoxy rmgs.

A further and specially preferred procedure for the preparation of dyestuffs or intermediates containing the group -R,Z-R consists in the two-sided linkage of the azo dyestuff residues containing at least one active hydrogen atom bound to the nitrogen atom directing coupling, or of coupling components H- A,NHR, and HA,NHR, with a diepoxide compound, for example, of the kind commercially available in epoxy resin chemistry. When a diglycidyl compound is used, a compound is obtained in which the symbols in the group -R,-ZR have the following meanings: R, and R are propylene groups which contain a hydroxyl group in fi-position to the nitrogen atom directing coupling and Z is the residue of a diglycidyl compound free from glycidyl groups.

When the cycloaliphatic epoxy compounds described below in which the epoxy oxygen atoms are bound directly to a cycloaliphatic ring are used as starting materials, the alkylene residues R, and R in the group R,-ZR are constituents of an alicyclic ring system and they also each contain a hydroxy group in fi-position to the nitrogen atom directing coupling which is formed by the opening of the epoxide rings, which hydroxy] group can be subsequently acylated in a manner such that it bears the same acyl substituents as the alkyl groups R, and R, when they are acylated in B-position.

Accordingly, the preferred compounds of the invention are disazo dyestuffs of the fonnula (l) in which at least one, but preferably both, diazo component residues D, and D, can be quaternated, and the coupling component has the meaning given above, and in which the group R,Z-R, has been produced by additively combining a diepoxide with two coupling components or azo dyestuff residues containing at least one active hydrogen atom bound to the nitrogen atom directing coupling.

The reaction of amino groups present in the aromatic nucleus is one of the fundamental reactions in epoxy resin chemistry, and all aspects of it havetherefore been studied; for example, the work of Lee and Neville, Epoxy Resins" New York, 1957, and Houben-Weyl, Methoden der organischen Chemie", Vol. 14, Part 2, Stuttgart, 1963, pages 462-567. Reaction with other functional groups and the usual diepoxides used in epoxy resin technology has also been dealt with extensively.

Reaction between epoxy groups and amino groups can even take place at room temperature, although temperatures within the range of from 30 to [50 C would be employed in the case of amino groups in the aromatic nucleus.

The reaction proceeds in a manner such that the two epoxy groups of the formula I6 react with the free amino hydrogen atom of the group of the formula H-NR- to form the B-hydroxyamine of the formula R being one of the residues R, or R, Disazo dyestuffs which are derived from an N,N-diglycidyl-alkylamine as middle component -R,Z-R., for example, N,N- diglycidylpropylamine, may also be obtained in that an alkylamine is reacted with double the molar amount of a monoazo dyestufl' of the general formula D-N N-AN( R)CH,CH(OH )--CH,-Y or equivalent amounts of a dyestufl of the formula and a dyestuff of the formula are reacted together, and, previously or subsequently, the fourth group R, is fused to the quatematable nitrogen atom with an alkylating agent R,Y, the symbol Y representing an easily eliminable negative residue capable of being replaced in alkylating reactions, especially a chlorine, a bromine or an iodine atom.

When the starting materials used in the preparation of the dyestufis of the formula (1) in accordance with the invention are monoazo dyestuffs of the formulae in which the groups B, and E, are groups containing reactive oxirane rings, it is preferable to start from the corresponding N-glycidyl compounds, or to use the corresponding N-y-chloro- (or -bromo)-B-hydroxypropyl derivatives, which are equivalent to the N- glycidyl compounds.

Monoazo dyestuffs of the kind mentioned are described in British Pat. Specifications Nos. 919,424, 856,898 and 868,468.

The following are given as examples of members of the well-known class of diepoxides or epoxy resins:

Alicyclic polyepoxides in which at least one epoxy group is attached to the alicyclic ring, for example, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis-(2,3-epoxycyclopentylether, ethyleneglycol-bis-(3,4-epoxytetrahydrodicyclopentadien-8-yl )-ether, 3 ,4-epoxytetrahydrodicyclopentadien-8-yl)-glycidylether; compounds having two epoxycyclohexyl residues bound through ester or acetal linkages, for example, diethyleneglycol-bis-( 3,4-epoxycyclohexanecarboxylate) his ?,4-(epoxycyclohexylmethyl)-succinate, 3,4- epoxy-6-methyl-cyclohexylmethyl- 3,4-epoxy-6- methylcyclohexanecarboxylate, as well as the acetal derived form 3,4-epoxyhexahydrobenzaldehyde and 3 ,4-epoxycyclohexanel l -dimethanol.

It is preferable to use bifunctional compounds. having two terminal epoxy groups, for example, lthe diglycidylethers of dehydricalcohols, for. example, glycoldiglycidylether, the diglycidyletl'ters *of dihydric phenols, for example, 4,4'dihydroxy-diphenylmethane, -dimethyimethane or -sulphone, the diglycidylethers obtained from, polyhydric :thiols, for example, bis-(mercaptomethylybenzenes, the MN- diglycidyl compounds, for example, of N,N'-dimethyl- 4,4'-diaminodiphenylmethane, ethyieneurea, 5,5- dimethylhydantoin, or oxamide, and the diglycidylesters of aliphatic, cycloaliphatic ortaromatic dicarboxylic acids, for example, phthalicraeiddnexahydrophthalic acid, tetrahydrophthalictacid .on-succinic acid, it being expedient to acylatetiftenthe reaction, especially after the reactionwith adiglycidylester.

Thus, disazo dyestufl's of the inwentionare obtained in which the divalent bridging group-Zjsformedyby the two-sided addition of an amino ,group idirecting coupling containing an actiwehydrogenetomvtonn' epoxy compound, especially ail digiycidylucornpound, and the groups R, and R represent "Nrflehydmxyethylene groups formed by the-openingofltheoxirane rings, the hydroxyl groups fonnedby itheopening-Offlte oxirane rings advantageously being'substitutedcespecially acylated.

Bifunctional coupling components suitabietorthe reaction with the diazonium compounds-oftheionmula D,N N-Cl andlor'D,-N ="N--Cl.are;'forempie, the following compounds, which, however, are preferably not coupled with heterocyclic 3M0! quatematable diazo components:

Calls coupiing eomponents which are specially preferredwhieh can 'alsobe eoupled'with hetero- A cyclic-indict? qmmat'able dim com onents fire, for mmplep the followingdiemh'es --which contain a 5 group which may be acyla'ted in position to each ot the nitrogen atoms directing coupling:

II: rEuritheibifimctionalccupling componentswhich-can be -..coupied heteeocyelic andlcr quaternamble 25 these diimines which contain'at leastonemeylggmup'in the 1w 'igroupwt'or-example,

. N/ c i Coupling of the 'bifunctional coupling componentsmay advantageously be effected in the presence of a coupling accelerator, for example, formamide, dimethylformamide and pyridine.

A preferred class of new disazo dyestuffs of the formula (l) is distinguished by the fact the diazo component residues of the formulae D, and D,- are free from quaternatable nitrogen atoms and that preferably the bridging group without dyestuff characteristics of the formula 2 does not contain an acyl group and/or contains at most one N,B-hydroxyethyl or -propyl group and/or does not represent a SO, group.

Of these dyestuffs, special mention is made of those in which the diazo component residues D, and D, are derived from a negative substituted monoaminobenzene which is free from further unsubstituted or possibly substituted amino groups.

When the bifunctional coupling component of the formula is coupled with less than 2 mols of a diazonium compound of the formula D-N N-Cl, a mixture is formed which constitutes a mixture of the dyestuffs of the invention and monoazo dyestuffs, which likewise come within the scope of the invention. Quaternation of the new disazo dyestuffs of the formula (l) in accordance with the invention can be carried out when the divalent bridging group 2 present in the said dyestuffs is free from ether bridges, especially phenolether bridges, and when preferably no C N- C bonds interrupt the carbon chain of the bridging group Z, which group, however, should be interrupted by at least one hetero atom, preferably at least one acyl group. Generally, the finished disazo dyestuffs may be used, which, for this purpose, are treated with esters of strong mineral acids or organic sulphonic acids, for example, dimethyl sulphate; alkyl or aralkyl halides, for example, methyl bromide or benzyl chloride; methanesulphonic acid methylesters or esters of benzenesulphonic acids that may be substituted, for example, 4-, 4-chloroor 4-nitrobenzene sulphonic acid ethyl ester. Alkylation is preferably effected by heating in an inert organic solvent, for example, xylene, carbon tetrachloride, ortho-dichlorobenzene or nitrobenzene. However, other solvents may also be used, for example, acetic anhydride, dimethylfonnarnide, acetonitrile or dimethylsulphoxide. The quaternated dyestuffs preferably contain as anion the residue of a strong acid, for example, sulphuric acid or a semi-ester thereof or a halogen ion, but they can also be used as double salts, for example, with zinc chloride, or as free bases.

Diamines of the formula in which R, and R, each represents a hydrogen atom or preferably an alkylene group, R, and R, each represents an alkylene group, 2, represents a divalent residue which contains at least one, but preferably at least two, acyl groups or a diacyl residue as divalent groups in the main chain which joins the nitrogen atoms together, and H-A, and A,,l-l are phenylene or naphthalene residues, are also included in the invention.

These diarnines may be obtained when the acylation processes described above are carried out with bifunc tional compounds, but the dyestuff component is replaced by the corresponding coupling components of the formulae in which HA,, l-l-A,, R,, R R, and R, have the meanings given above and X, and X, each represents a group containing at least one reactive hydrogen atom, preferably an amino, a mercapto or a hydroxyl group.

The dyestufls described above, mixtures thereof, and mixtures of these dyestufi's and other azo dyestuffs, especially when converted into a finely divided form, for example, by grinding, pasting, reprecipitation and so forth, are eminently suitable for dyeing and printing synthetic fibers, for suitable acrylic fibers and acrylonitrile fibers, fibers made from polyacrylonitrile and copolymers of acrylonitrile and other vinyl compounds, for example, acylic esters, acrylamides, vinylpyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, as well as acrylonitrile-block polymers, fibers made from polyurethanes, cellulose triacetate and cellulose (2%) acetate, polyamides, for example, nylon 6, nylon 6.6 or nylon 12, and especially fibers made from aromatic polyesters, for example, those made from terephthalic acid and ethylene glycol or l,4-dimethylolcyclo-hexane, and copolymers of terephthalic and isophthalic acid and ethylene glycol.

The present invention therefore also includes a process for dyeing or printing synthetic fibers, especially polyester fibers, wherein there are used water-insoluble disazo dyestuffs which are free from carboxyl and sulphonic acid groups and which correspond to the fonnula in which R, and R, each represents a hydrogen atom or a substituted alkyl group, each of which may be bound to residues A, and A, respectively in ortho-position to the nitrogen atoms directing coupling to form a ring, R, and R each represents an alkylene group which binds the nitrogen atom to 2 preferably through at least 2 carbon atoms, the groups -NR,R,,- ZR,-NR,, NR,-,Z or -NR,R,Z-being capable of forming a perhydropyrazine residue, A, and A, each represents a para-phonylene residue, D, and D, each represents the residue of a diazo component free from quatemated atoms and 2 represents a divalent bridging group preferably containing at least one hetero atom and which does not have dyestuff characteristics, mixtures of such dyestuffs and mixtures of the said dyestuffs and other azo dyestuffs.

Preferably, the nitrogen atoms directing coupling are joined together through at least five atoms.

One case in which the nitrogen atoms directing coupling present in the dyestuffs used are joined together by fewer than five atoms is that of the in which X;, represents a hydroxyl group or a bromine or a chlorine atom and R,, R,, A A12, D and D, have the meanings given above.

The dyeing process is preferably carried out with those dyestuffs in which the colorless bridging group Z does not contain an acyl group and in which the residues R, and R, contain at most one B-hydroxyethyl or -propyl group.

Of the dyestuffs which contain sulphur, preference is given to those in which the residue Z does not contain a group of the formula Cl-l,-CH,-SO CH,CH,.

When the above-mentioned new dyestuffs of the formula 1) contain one or two quatemated diazo residues of the formula D, and/or D they are eminently suitable for dyeing fibers and fabrics of the polyacrylic type. In this field of application preference is given to those dyestufi's in which the residue 2 contains at least one acyl residue and/or the residues R, and R are N-B- hydroxyethylor -propyl groups that may be acylated.

Dyestuffs that are specially suitable for dyeing acrylic fibers, that is to say, fibers synthesized at least in part from acrylonitrile or dicyanoethylene, are the water-insoluble dyestuffs free from quaternary groups and in which the bridging group Z contains one or more amino groups which are not bound aromatically, that is to say, which are not bound to an aromatic ring and which are not present in such a ring.

For dyeing, the water-insoluble, non-quaternated dyestuffs are advantageously used in a finely divided form and in the presence of a dispersing agent, for example, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents. Prior to dyeing it is generally advantageous to convert the dyestuff into a dyeing preparation which contains a dispersing agent and the finely divided dyestuff in a form such that a fine dispersion is formed when the preparation is diluted with water. Such dyestuff preparations may be obtained in known manner, for example, by grinding the dyestuff presence the dry or wet state in the pesence or absence of a dispersing agent.

To obtain stronger dyeings, for example, on polyethylene terephthalate fibers, it is advantageous to add a swelling agent to the dyebath, or to carry out the dyeing process under superatrnospheric pressure at a temperature of above 100 C, for example, at 120 C. Suitable swelling agents are aromatic carboxylic acids, for example, benzoic acid or salicylic acid, phenols, for example, orthoor para-hydroxydiphenyl, aromatic halogenated compounds, for example, chlorobenzene, orthodichlorobenzene or trichlorobenzene, phenylmethylcarbinol or diphenyl. When carrying out the dyeing process under superatmospheric pressure, it is generally advantageous to render the dyebath slightly acid, for example, by the addition of a weak acid, for example, acetic acid.

The non-quaternated, water-insoluble dyestuffs to be used in accordance with the invention are specially suitable for application by the so-called thermofixation process in which the fabric to be dyed is impregnated preferably at a temperature not exceeding 60 C with an aqueous dispersion of the dyestuff which advantageously contains 1 to 50 percent of urea and a thickening agent, especially sodium alginate, and squeezed in the usual manner. The fabric is advantageously squeezed so as to retain S0 to percent of its dry weight of dye-liquor.

To fix the dyestuff, the fabric so impregnated is heated to a temperature of above 100 C, for example, to a temperature between and 210C, preferably after drying, for example, in a current of warm air.

The above-mentioned thermofixation process is specially suitable for dyeing union fabrics made from polyester fibers and cellulosic fibers especially cotton. In this case, the padding liquor contain, in addition to the non-quaternated, water-insoluble dyestuff to be used in accordance with the invention, dyestuffs which are suitable for dyeing cotton, for example, direct dyestuffs or vat dyestuffs, or especially the so-called reactive dyestufls, that is to say, dyestuffs that can be fixed on the cellulosic fiber with formation of chemical bond, for example, dyestuffs which contain a chlorotrian'ne or a chlorodiazine residue. In the latter case it is advantageous to add an agent capable of binding acid to the padding solution, for example, an alkali metal carbonate or an alkali metal phosphate or an alkali metal borate or perborate, or a mixture thereof. When using vat dyestuffs, the padded fabric has to be treated alter the heat treatment with an aqueous alkaline solution of one of the reducing agents commonly used vat dyeing.

The dyeings produced on polyester fibers by the said proces are advantageously subjected to an after-treatment, for example, by heating with an aqueous solution of a non-ionic detergent.

The dyestufi's may also be applied by printing processes. In this method of application of printing paste, for example, is used which contains the finely divided dyestuff, if necessary, in admixture with one of the above-mentioned cotton dyestuffs, as well as the adjuvants normally used in printing, for example, wetting and thickening agents, if necessary, in the presence of urea and/or an agent capable of binding acid.

The processes indicated produce strong dyeings and prints possessing excellent properties of fastness, especially good fastness to light, sublimation, decatizing, washing and chlorinated water. Dyeings on acetate rayon are also distinguished by good fastness to gas fading. A further advantage of the dyestuffs to be used in accordance with the invention is that they reserve well on wool and cotton.

Dyeing acrylic fibers, that is to say, fibers synthesized at least in part from acrylonitrile or dicyano-ethylene, is specially advantageously effected with those waterinsoluble members of the above group of dyestuffs in which the group Z contains one or more amino groups that are not bound aromatically, that is to say, that are not bound to an aromatic ring or are not present in a ring when the said ring greatly reduces the basicity of the nitrogen atom.

The new water-insoluble non-quatemated dyestuffs may also be used for the spin-coloration of polyamides, polyesters and polyolefines. The polymer to be colored is advantageously admixed with the dyestuff in the form of a powder, grains or chips, as a solution ready for spinning or in the form of a melt; the dyestuff may be in the dry state, or in the form of a dispersion or a solution in a solvent which may be volatile. After the dyestuff has been homogeneously dispersed in the polymer solution or melt, the mixture is processed in known manner into fibers, yarns, monofilaments, films and so forth is known manner, for example, by casting, moulding or extruding.

The new quaternated dyestuffs or dyestufi salts are suitable for dyeing and printing a very wide variety of synthetic fibers, for example, polyvinyl chloride, polyamide and polyurethane fibers, and also polyester fibers, for example, polyethylene terephthalate fibers, but especially polyacrylo-nitrile fibers or polyvinylidene cyanide fibers and copolymers thereof with other monomers.

The new dyestuffs are also suitable for coloring polymerization products of acrylonitrile, polyolefines and other plastics by addition to the composition prior to the shaping operation, and they may also be used for coloring oil paints and lacquers. The above-mentioned thermofixation process may also be applied.

Some of the new products are also valuable pigments which may be used for a very wide variety of purposes. For example, they may be used in a state of fine division for the spin-coloration of filament and staple-fiber viscose and cellulose ethers and esters, and also in the production of colored lacquers and lake-formers, solutions or products made from cellulose acetate, nitrocellulose, natural or synthetic resins, for example, polymerization resins or condensation resins, for example, aminoplasts, alkyd resins, phenoplasts and polyolefines, for example, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicones and silicone resins.

The following Examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

Preparation of the bifunctional coupling components Procedure I 48.8 Parts of N-ethyl-N-(B-hydroxyethyl)-metatoluidine in 30 parts by volume of anhydrous nitrobenzene are stirred together with 11 parts of metallic sodium for 15 hours while heating under reflux. The excess of sodium is removed and then 53.8 parts of N-ethyl-N-(Bchloroethyl)-meta-toluidine in 50 parts by volume of anhydrous benzene and 4 parts of 45 sodium iodide are added. The mixture is stirred for a prolonged period under reflux and is then diluted with anhydrous benzene. The sodium chloride and sodium iodide formed are removed by filtration and the filtrate is concentrated and distilled. It boils within the range of 50 from [85 to 195C under a pressure of 0.1 mm Hg. The amine so obtained corresponds to the formula CH CH3 HsC:

is obtained in the form of a yellow, viscous oil boiling at l50to lC/0.01 mm Hg. Procedure [I 36 Parts of N-ethyl-N-(B-hydroxyethyl)-metatoluidine, together with 12.5 pans of carbonic acid diethyl ester and 0.2 part of sodium, are slowly heated to 170 C in an oil bath while stirring, in which process ethanol is distilled. After some time, the batch is allowed to cool, the residue is dissolved in benzene and extracted with water. The benzene phase is dried, the benzene is evaporated and the crude product is distilled. 18.2 Parts of a pale yellow oil boiling at 195 to 205 C/0.02 mm Hg and corresponding to the formula Ulla are obtained.

Analysis: Calculated: C 71.8% H 8.4% N 7.3% Found: C 72.3% H 8.4% N 7.2%.

Procedure III 50 Parts of N-ethyl-N-(B-hydroxyethyl)-aniline and 26 parts of toluylene-2,4-diisocyanate are heated in a bath at to C in 50 parts of anhydrous benzene. On cooling, 73.3 parts of the crude product precipitate in the form of colorless crystals melting at 108 to C. After one recrystallization from methanol, the melting point is ll3to 116 C.

The product corresponds to the formula CiHs Analysis: Calculated: C 69.0% H 7.2% N 11.1%

Found: C 69.1% H 6.9% N 11.5% Procedure IV By using 54 parts of N-ethyl-N-(B-hydroxyethyhmeta-toluidine, 25 parts of hexarnethylene-1,6-diisocyanate and 50 parts of benzene and following the procedure described in Procedure ll, there are obtained, after the addition of 80 parts of ethyl alcohol and cooling, 46 parts of a crude product melting at 58 to 60 C. The product corresponds to the formula Analysis: Calculated: C 68.4% H 8.8% N 10.6%

Found: C 68.4% H 8.6% N 10.5%. Procedure V 19 Parts of N-B-hydroxyethyl-N-B-cyanoethylaniline in 100 parts of chlorobenzene are added dropwise to 100 parts of chlorobenzene saturated with phosgene at a temperature of C. The batch is stirred for three hours at that temperature while continuously introducing phosgene. The batch is then heated to about 50 to 55 C, stirred for about 30 minutes at that temperature and then heated to 80 to 85 C. Phosgene is introduced at that temperature, while stirring. until a clear solution forms. The excess of phosgene is then blown out with nitrogen and the hot solution is filtered. This solution is added to 19 parts of N-B-hydroxyethyl-N-ficyanoethylaniline and the whole is treated for 24 hours under reflux while stirring. The solvent is then completely removed in vacuo, and ml of ethanol are added to the residue. After two to three days, most of the residue has solidified. After filtration, the residue is triturated with cold ethanol and isolated by filtration. Alter recrystallization, a product of the formula Analysis: Calculated: C 67.96% H 6.45% N 13.79%

Found: C 68.21% H 6.37%N 13.56% Procedure VI 30 parts of N-ethylaniline, 17.1 parts of fly,B',-y'- diepoxytripropylamine (prepared in accordance with French Patent Specification No. 1,137,175). 30 parts by volume of chlorobenzene and 10 drops of triethylamine are stirred for 30 hours at 140 to 150C. The solvent is then removed in vacuoand the residueis distilled in a high vacuum. The B,.B'-dihydroxy-'y;y'-di- (N-phenyl-N-ethylamino)-tripropylamine of the formula is obtained in the form of a viscous oil.

Analysis: Calculated: C 72.60% H 9.51% N 10.16%

Found: C 72.3% H 9.7% N 10.2%

30 Parts of fi,B'-dihydroxy-'y,'y'-di-(N-phenyLN- ethyl-amino)-tripropylamnie are heated together with 100 parts by volume of acetic anhydride for three hours under reflux. The solvent is then removed in vacuo and the residue is distilled in a high vacuum. The 18,111- diacetoxy-y,-y'-di-(N-phenyl-N-ethylamino)- tripropylamine of the formula CIH5 is obtained in the form of an oil.

Analysis: Calculated: C 69.99% H 8.17% N- 8.44% Found: C 69.6% H 8.8%11 8.6% Procedure V11 20 Parts of N-ethylaniline, 15 parts of butanedioldigly-cidylether and 50 ml of chlorobenzene are stirred for 30 hours at to C. The solvent is then removed in vacuo and the residue is distilled in a high vacuum. An oily product of the formula is obtained.

Analysis: Calculated: C 70.23% H 9.07% N 6.30%

Found: C 70.0% H 8.9% N 6.3%

The product is subsequently acetylated with an excess of acetic anhydride and the reaction mixture on evaporation in vacuo yields the product of the formula The following bifunctional coupling components are prepared in an analogous manner. After acetylation. the acetylation products are used for the manufacture of disazo dyestuffs without further purification. This mode of working has the advantage that any excess of monoalkylaniline that may be present isconverted into the corresponding N-acyl derivative which has a much lower coupling capacity than the bifunctional coupling components and virtual does not participate in coupling under the coupling conditions subsequently described.

All the following products were obtained in the form of viscous oils,

vur

can-on i l CHr-CH-CHr-N (LC-H. 0

EXAMPLE 1 3.4 Parts of 2-cyano-4-nitroaniline are added in por- 2 tions to 30 parts of sulphuric acid monohydrate in which 1.4 parts of sodium nitrite have been dissolved. After some time, this diazo compound is discharged on to 150 parts of ice, the excess of nitrite is destroyed and a solution of 3.6 parts of carbonic acid-di-B-(phen- 30 higher than C. It dyes polyester fibers claret shades 35 possessing excellent fastness to light and sublimation.

The same dyestuff may be obtained by reacting 2 mols of N-{4-(2'-cyano-4'-nitrophenylazo)phenyll-N- ethylaminoethanol with 1 mo] of phosge'ne.

EXAMPLE 2 By following the procedure described in Example 1 and replacing the 3.6 parts of carbonic acid-di-B- (phenylethylamino)-ethyl ester with 4.1 parts of car- 45 bonic acid-di-{p-phenyLfi-cyanoethylaminol-ethyl ester, a dyestuff is obtained which dyes polyester red shades possessing excellent properties of fasmess.

EXAMPLE 3 By following the procedure described in Example I and replacing the 3.6 parts of carbonic acid-di-B- (phenylethylamino)-ethyl ester with 4.6 parts of succinic sessing excellent properties of fastness.

EXAMPLE 4 "all:

aciddi-[B-phenyl-B'-cyanoethylamino}-ethyl 60 ester, a dyestuff is obtained which dyes red shades pos- HlCr C, the batch is heated to 80 C within one hour while stirring, for two hours at 80 C, discharged on to ice while still warm, neutralized with a 10 percent sodium carbonate solution, taken up in benzene, the organic phase is washed with a sodium chloride solution, dried with calcium chloride; filtered and concen- 193 Parts of the product of the formula (I 115 H502 C N l. O \G c,rrru r icm).-ii-nofin Ha H! remain the ofa lirownoil.

1.64 Parts of Z eyanot-nitroaniIine are diazotized in the usual at 13 to C with N nitrosylsulphuric acid, the is onto ice and then with a small amount of sulphamic acid. A solutiohoi 2.3 dfthe product described in the preceding l in 20 by volume of glacial acid is added to this mixture a't'0" to 5 C while stirring, the batch is emigre at 0" to 5 C, the is isoittted by suction filtration, washed vh'th water until the washings run neutral and then dried in a vacuum cabinet at 40 C. 3.3 Parts of the dyestuff of the formula remain. lt dyes polyester material bluish red shades possessing good properties of lastness.

Example 5 50.9 Parts of N -fi-cyanoethyl-fi-hydroxyethylaniline are dissolved in 70 parts by volume of anhydrous benzene. 25 Parts of a-cltlorofumaric acid dichloride are added dropvrise to this solution, the batch is stirred 24.9 Parts of N-ethyl-N-2-methylaminoethyl-aniline under reflux for four hours, discharged on to a mixture (prepared from the para-tolucnesulphonic ester of N- ethyl-N-2-hydroxy-ethylaniline and methylamine) are dissolved in 50 parts by volume of pyridine; 12.8 parts of adipic acid dichloride are added dropwise at 10 to of ice and water, neutralized with sodium carbonate, the benzene phase is separated, dried with calcium chloride, filtered, and the filtrate is concentrated. 58.5 Parts of the product of the formula canon Nome.

CilIi() C=CH-g UCfiI4 (.l are obtained in the form of a dark oil. No starting material is detectable in a thin-layer chromatogram.

9.65 Parts of 2,6-dichloro-4-nitroaniline (94.6 percent) are diazotized at a temperature not exceeding 35 C in 44 parts by volume of N nitrosyl-sulphuric acid, and the batch is discharged on to a mixture of ice and water. 9.9 Parts of the product described above are dissolved in 200 parts by volume of acetone and then 40 parts by volume of water are added. The diazo component is added dropwise at -5 to C to this solution, the batch is stirred overnight at 0 C, the product is isolated by suction filtration, washed until the washings run neutral and dried. 17.7 Parts of the dyestuff of the formula I Cl (hHiCN are obtained which dyes polyester materials yellowbrown shades possessing excellent properties of fastness.

EXAMPLE 6 71.2 Parts of N-ethyl-N-3-arninopropylaniline (obtained by pressure-hydrogenation of N-ethyl-N-flcyanoethylaniline in liquid ammonia) and 43.6 parts of pyromellitic anhydride are melted together for some hours at 180 C. After cooling, the brown-red oil obtained is dissolved in 1,000 parts by volume of hot chloroform, the solution is cooled, the reddish crystalline mass is isolated by filtration, washed with chloroform and then dried in a vacuum cabinet. 60 parts of the product of the formula 0 0 Gills H H N Calls CN U can It IL 1 N '03;

i ll H NCHiC:

1 11 III IV 7 2-cyano-4-6-dinitro- N-p-hydroxyethyl-N-pphoegene violet aniline cyanoethyllniline 8 A-nitroaniline 9 2-cyano-4-nitroaniline terephthaloyldichloride red 1,6-hexamethyllene-dillored cyanate adiplc acid red dichloride orange I I u u l2 Z-ehloroJ-nitrophosgene orange aniline l3 2,6-dichloro-4-nitro N-ethyl-N-B-hy phosgene brown -a.niline droxyethylaniline N-fl-hydroxyethyi-N-fiyellowcyanoethylaniline brown 15 2-cyano-4-nitro- N-fi-hydroxyethyl toluylene aniline -N-B-cyanoethyl -2,4-dired -aniline isocyanate l6 thiophenered 2,5-dicarboxylic acid dichloride l7 N-ethyl-N-B-hytoluyleneviolet droxyethylaniline 2,4-diiaocynnate l8 N-ethyl-N- bexamethylene- B-hydnoxyethyl-S- 1,6-diisoviolet rnethylaniline cyanate l9 N-ethyl-Nfl-hyphosgene claret droxyethylaniline 20 Z-cyano-d-nitro-b- N-ethyl-N-B- N-B-chlorobluechloroaniline hydroxyethyl-J- ethyl-N- violet methylethyl-3-methylaniline aniline 21 2-cyano-4-nitro- N-ethyLN'fi- N-fl-chloroaniline hydroxyethyl-Iiethylviolet methyl- 3-methylaniline aniline 22 N-ethyland N-B phosgene red -cyanoethyl-N- (with N-fl- B-hydroxyethyl cyanoethyl- -aniline N-fl-hydroxyethylanilinechloroforrnic acid ester as intermediate product) 23 2-benzoyl-4,6- N-fl-cyanosuccinic red dinitroaniline ethyl-N-,8-hyacid droxyethylaniline dichloride 24 4-nitroaniline N-fl-ethyl-N-fiterephthalic red hydroxyethyl-3- acid dimethylaniline chloride 25 2,6-dichlom-4- claret nitroaniline 26 Z-chloro-d-nitroclaret aniline 27 4-nitroaniline 28 2-cyano-4-nitroaniline 29 2,6-dichloro-4- nitroaniline 30 4-nitroaniline 3l 2-chloro-4-nitroaniline 32 2,6-dichloro-4- nitroaniline 3 3 4-nitroaniline 34 2-cyano-4-nitroaniline 35 2.6-dichloro-4- nitroaniline 36 2cyano-4-nitroaniline 37 2,6-dichloro-4- nitroaniline 38 4-nitroaniline 39 2-cyano-4-nitroaniline 40 A-nitroaniline 4 l 2-cyano-4-nitroaniline 42 Z-chloro-d-nitro aniline 43 2-chloro-4-methyisulphonylaniline 2,6-pyridinedicarboxylic red acid dichloride N-p-ethyl-N- 2,6-p-ytidine- B-hydroxyethyl dicerboxylic violet -3-methylacid aniline dichloride isophthalic brownacid orange dichloride claret phthllic brown acid dichloride (CLCO 'h ds (CLCO CHfiI-LLS violet mm -hydroxyethyl ac aniline dichloride N-p'cyanoethybhhfiyellowhydroxyethylanil'ine brown N-runinopropyl-N- scarlet ethylaniline N-B-cyano- Z-chlortr -fl-hydroxyformic acid red ethyllniline dichloride fumaric acid orange dichloride N-benzyl-N-B-hy- N-benzyl ruby droxyethyh fi-chloroethylaniline aniline ll ll yellow 44 2-cyano-4-nitroaniline nitrosylsulphuric acid, the batch is stirred for one hour, discharged on to ice and sulphamic acid is added. A solution of 3.32 parts of bis-[Z-(meta-toluidino )-ethyl]- sulphone (made in accordance with Example 3 of British Pat. Specification No. 1,076,380) in parts by volume of glacial acetic acid is added to this mixture at 0 C, whereupon the dyestuff of the formula EXAMPLE 47 3.3 Parts of 2-cyano-4-nitroaniline are diazotized at 20 C in 20 parts by volume of N nitrosylsulphuric acid, and the batch is discharged on to 200 parts of ice. A solution of 4.9? parts of B,fl'-diacetosyy,y'-di-( N phenyl-N-ethyl)-aminotriptopylpropane in 50 parts by volume of dimethylformamide is added dropwise to this solution at a temperature not exceeding 10 C, the batch is stirred for 3 hours, neutralized with 30 percent sodium hydroxide solution and then stirred overnight. The dycstuff is then isolated by filtration and dried in vacuo. The dyestufi' so obtained corresponds to the formula isophthalic violet -droxyaniline acid chloride thiopheneviolet 2,5-dicarboxylic acid dichloride EXAMPLE 46 4.4 Parts of 2,6-dichloro-4-nitroaniline are introduced at 25 to 30 C into 20 parts by volume of N and dyes polyester fibers ruby shades. It also produces ruby shades of good fastness to light on polyacrylonitrile.

By coupling a diam compound of the components listed in Column l of the be following Table with the coupling components listed in Column II, dyestuffs are obtained which dye polyester the shades listed in column "I and polyacrylonitrile the shades listed in Column IV.

1 ll III IV is CN Rub l (hHr-OII M- 2N N U: N

CHr-()3 --CHrO- it! Same as tlllOVt' ll -(F-(l 0-4111; Red

-(CH2)F N CH -(IJIP-CHPO (l-C ()C H! I2 50 ......llo (2 H; Violet...

EXAMPLE 62 3.45 Parts of 2-chloro-4-nitroaniline are suspended in 40 parts by volume of water and 6 parts by volume of concentrated hydrochloric acid, the suspension is cooled to 0 C and diazotization is effected with 6 parts 37 38 time. ihe D is adjusted t 6 i0 7 y the addition of is obtained which dyes polyester fibers orange shades sodium hydroxide solution and the dyestuff solution is possessing d fa t t sublimation.

stirred for a short period. The dyestufi' is then precipitated by the addition of a mixture of ice and water. The dyestuff is separated from the aqueous solution by centrifuging and dried in vacuo. A product of EXAMPLE 64 the formula 3.22 Parts of sodium nitrate are introduced into 21.5

is obtained which dyes polyester and polyacrylonitrile parts by volume of concentrated sulphuric acid. The

red Shades i5 batch is heated at 65 C until a clear solution forms,

Preparation of the Bifunctiona] Component whereupon the solution is cooled to 0 to 5 C and a 256 Parts of the toluenesulphonic ester of N-ethyl-N- mixture of 36.8 parts by volume of glacial acetic acid B-hydroxyethyl-aniline, 290 parts of ethanol and 80 and 6.13 parts by volume of propionic acid is added parts of 35 percent aqueous methylamine solution are dfopwise, during which the temperature must not be stirred for 2 hours under reflux at 80 C. The reaction lowed to rise above isoc- The batch is again cooied mixture is evaporated under reduced pressure, the C P of y residue is suspended in water, the suspension is made are added at that p and a mixture of strongly alkaline with 100 parts of concentrated sodi- [Jims by Voiume of glacial acetic acid and um hydroxide solution and then extracted with P8113 y Volume of Propionic acid is again The chloroform. After drying, the chloroform solution is batch is then stirred for three hours at to a evaporated over l i d di l h d the small amount of solid sulphamic acid is added and stirresidue is then distilled in a high vacuum. After removring is continued in the first runnin the com and of the formula g gs po 30 This solution is added dropwise at a temperature not am m exceeding 10 C to a solution of 9.2 parts of the diester O: cm N- derived from 1 mol of succinic acid dichloride and N-B- LV hydroxyethyl-N-B-cyanoefl'iylaniline in 400 parts by volume of acetone. This solution is stirred overnight at IS obtained In the form of a practically colorless oil boila temperature of o to C whereupon the dyesmfiis 2 at iC/0'04 mm precipitated by the addition of a mixture of ice and water. It is isolated by filtration and washed with water EXAMPLE 63 until the washings run neutral. The dyestutf is then 3.88 Parts of 2amino-6-ethoxybenzthia1ole are dried in vacuo. A dyestuff of the formula diazotized at 0 to 5 C in 20 parts by volume of N is obtained which dyes polyester fibers an orange nitrosylsulphuric acid in the presence of glacial acetic Shadeacid and propionic acid, and the solution obtained is EXAMPLE added dropwise at a temperature not exceeding l0 C 50 By f ll i th procedure d ib d i h dto a solution of 4.06 parts of the carbonic acid diester ing Exam le and replacing the 8.2 parts of 2-amino-6- of N,fl-cyanoethyl-N-fi-hydroxyethylaniline in ml ethoxybenzthiazole with 7.5 parts of 3-phenyl-5- of dimethylfonnamide. The batch is then stirred overaminothia-diazole, a dyestuff of the formula 0 H (J- i 0211 ON NCH 0 NCC H i u in 41 t i i N CN=N N N- -N N- C'JlIr-U-C-CH?CH:T' C"0C! 4 E ii I night at 0 to 5 C, neutralized with 30 percent sodium 60 is obtained which dyes polyester fibers an orange hydroxide solution, and the dyestufi is precipitated by shade.

the addition of water. After filtration and drying in The dyestuffs corresponding to the following formuvacuo, a dyestuff of the formula las may be obtained in an analogous manner: 

2. A dyestuff according to claim 1 of the formula
 3. A dyestuff according to claim 1 of the formula
 4. A dyestuff according to claim 1 of the formula
 5. A dyestuff according to claim 1 of the formula 